The present invention relates to novel reactive colorants and mixtures of reactive colorants, to processes for their production and to their use.
The practice of dyeing using reactive dyes has recently led to higher demands being made of the quality of the dyeings and the profitability of the dyeing process. As a result, there is still a need for novel reactive dyes having improved properties, especially in respect of their application.
Dyeing nowadays requires reactive dyes that have sufficient substantivity and at the same time have good ease of washing off of unfixed dye. They should also have a good tinctorial yield and high reactivity, the objective being to provide especially dyeings having high degrees of fixing. The known dyes do not satisfy these requirements in all properties.
The problem underlying the present invention is accordingly to find, for the dyeing and printing of fibre materials, novel improved reactive dyes and mixtures of reactive dyes that possess the qualities characterised above to a high degree. The novel dyes and dye mixtures should especially be distinguished by high fixing yields and high fibre-dye binding stability; it should also be possible for dye that is not fixed to the fibre to be washed off easily. The dyes should also yield dyeings having good allround properties, for example fastness to light and to wetting.
It has been shown that the problem posed is largely solved by the novel dyes and dye mixtures defined below.
The present invention accordingly relates to dyes of formula (1) 
wherein
R1 and R2 are each independently of the other hydrogen or C1-C4alkyl, and
D1 and D2 are each independently of the other a radical of formula (2) 
xe2x80x83wherein
(R3)0-3 denotes from 0 to 3 identical or different substituents selected from the group halogen, C1-C4alkyl, C1-C4alkoxy, carboxy, nitro and sulfo, and
X1 is a radical of formula (3a), (3b), (3c), (3d), (3e) or (3f)
xe2x80x94SO2xe2x80x94Zxe2x80x83xe2x80x83(3a),
xe2x80x94NHxe2x80x94COxe2x80x94(CH2)mxe2x80x94SO2xe2x80x94Zxe2x80x83xe2x80x83(3b),
xe2x80x94CONHxe2x80x94(CH2)nxe2x80x94SO2xe2x80x94Zxe2x80x83xe2x80x83(3c),
xe2x80x94NHxe2x80x94COxe2x80x94CH(Hal)xe2x80x94CH2xe2x80x94Halxe2x80x83xe2x80x83(3d),
xe2x80x94NHxe2x80x94COxe2x80x94C(Hal)xe2x95x90CH2xe2x80x83xe2x80x83(3e) or 
xe2x80x83wherein
Y is halogen, T independently thereof has a meaning given for Y or is a non-fibre-reactive substituent or is a fibre-reactive radical of formula (4a), (4b), (4c), (4d) or (4e)
xe2x80x94NHxe2x80x94(CH2)2-3xe2x80x94SO2xe2x80x94Zxe2x80x83xe2x80x83(4a),
xe2x80x83xe2x80x94NHxe2x80x94(CH2)2-3xe2x80x94Oxe2x80x94(CH2)2-3xe2x80x94SO2xe2x80x94Zxe2x80x83xe2x80x83(4b), 
xe2x80x83wherein
Z is vinyl or a radical xe2x80x94CH2xe2x80x94CH2xe2x80x94U and U is a group removable under alkaline conditions,
Zxe2x80x2 is a group xe2x80x94CH(Hal)xe2x80x94CH2xe2x80x94Hal or xe2x80x94C(Hal)xe2x95x90CH2,
m and n are each independently of the other the number 2, 3 or 4, and
Hal is halogen.
As C1-C4alkyl for R1 and R2, each independently of the other, there come into consideration, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, especially methyl and ethyl.
Preferably, one of the radicals R1 or R2 is hydrogen and the other is methyl or ethyl.
Special preference is given to R1 and R2 as hydrogen.
As halogen for R3 there come into consideration, for example, fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, and especially chlorine.
As C1-C4alkyl for R3 there come into consideration, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, preferably methyl and ethyl, and especially methyl.
As C1-C4alkoxy for R3 there come into consideration, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy, preferably methoxy and ethoxy, and especially methoxy.
Preferably, T is a non-fibre-reactive substituent or is a fibre-reactive radical of formula (4a), (4b), (4c), (4d) or (4e).
If T is a non-fibre-reactive substituent, it may be, for example, hydroxy; C1-C4alkoxy; unsubstituted or hydroxy-, carboxy- or sulfo-substituted C1-C4alkylthio; amino; amino mono- or di-substituted by C1-C8alkyl, wherein the alkyl is unsubstituted or is further substituted, e.g. by sulfo, sulfato, hydroxy, carboxy or by phenyl, especially by sulfo or by hydroxy and is uninterrupted or interrupted by an xe2x80x94Oxe2x80x94 radical; cyclohexylamino; morpholino; Nxe2x80x94C1-C4alkyl-N-phenylamino or phenylamino or naphthylamino, wherein the phenyl or naphthyl is unsubstituted or substituted, e.g. by C1-C4alkyl, C1-C4alkoxy, carboxy, sulfo or by halogen.
Examples of suitable non-fibre-reactive substituents T include amino, methylamino, ethylamino, xcex2-hydroxyethylamino, N-methyl-N-xcex2-hydroxyethylamino, N-ethyl-N-xcex2-hydroxyethylamino, N,N-di-xcex2-hydroxyethylamino, xcex2-sulfoethylamino, cyclohexylamino, morpholino, 2-, 3- or 4-chlorophenylamino, 2-, 3- or 4-methylphenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or 4-sulfophenylamino, disulfophenylamino, 2-, 3- or 4-carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 4,8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino, methoxy, ethoxy, n- or iso-propoxy and hydroxy.
As non-fibre-reactive radical, T is preferably C1-C4alkoxy, unsubstituted or hydroxy-, carboxy- or sulfo-substituted C1-C4alkylthio, hydroxy, amino, N-mono- or N,N-di-C1-C4-alkylamino unsubstituted or substituted in the alkyl moiety by hydroxy, sulfato or by sulfo, morpholino, or phenylamino or Nxe2x80x94C1-C4alkyl-N-phenylamino (wherein the alkyl is unsubstituted or substituted by hydroxy, sulfo or by sulfato) wherein the phenyl ring is in each case unsubstituted or substituted by sulfo, carboxy, acetylamino, chlorine, methyl or by methoxy, or naphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups.
Especially preferred non-fibre-reactive radicals T are amino, N-methylamino, N-ethylamino, N-xcex2-hydroxyethylamino, N-methyl-N-xcex2-hydroxyethylamino, N-ethyl-N-xcex2-hydroxyethylamino, N,N-di-xcex2-hydroxyethylamino, xcex2-sulfoethylamino, morpholino, 2-, 3- or 4-carboxyphenylamino, 2-, 3- or 4-sulfophenylamino or Nxe2x80x94C1-C4alkyl-N-phenylamino.
In the case of the fibre-reactive radicals T of formulae (4a) and (4b), Z is preferably xcex2-chloroethyl. In the case of the fibre-reactive radicals T of formulae (4c) and (4d), Z is preferably vinyl or xcex2-sulfatoethyl.
If T is a fibre-reactive radical, T is preferably a radical of formula (4c) or (4d), and especially of formula (4c).
Hal in the fibre-reactive radicals of formulae (3d), (3e) and (4e) is preferably chlorine or bromine, especially bromine.
Y in the fibre-reactive radical of formula (3f) is, for example, fluorine, chlorine or bromine, preferably fluorine or chlorine, and especially chlorine.
As a leaving group U there come into consideration, for example, xe2x80x94Cl, xe2x80x94Br, xe2x80x94F, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3, xe2x80x94OPO3H2, xe2x80x94OCOxe2x80x94C6H5, xe2x80x94OSO2xe2x80x94C1-C4alkyl and xe2x80x94OSO2xe2x80x94N(C1-C4alkyl)2. U is preferably a group of formula xe2x80x94Cl, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3, xe2x80x94OCOxe2x80x94C6H5 or xe2x80x94OPO3H2, especially xe2x80x94Cl or xe2x80x94OSO3H, and more especially xe2x80x94OSO3H.
Examples of suitable radicals Z accordingly include vinyl, xcex2-bromo- or xcex2-chloroethyl, xcex2-acetoxyethyl, xcex2-benzoyloxyethyl, xcex2-phosphatoethyl, xcex2-sulfatoethyl and xcex2-thiosulfatoethyl. Z is preferably vinyl, xcex2-chloroethyl or xcex2-sulfatoethyl.
D1 and D2 preferably are each independently of the other a radical of formula (2a), (2b), (2c), (2d) or (2e) 
especially of formula (2a) or (2e), wherein
(R3a)0-2 denotes from 0 to 2 identical or different substituents selected from the group halogen, C1-C4alkyl, C1-C4alkoxy and sulfo, especially methyl, methoxy and sulfo,
X1a is xcex1,xcex2-dibromopropionylamino or xcex1-bromoacryloylamino,
m is the number 2 or 3, especially 3,
n is the number 2 or 3, especially 2, and
Z1, Z2, Z3 and Z4 are each independently of the others vinyl, xcex2-chloroethyl or xcex2-sulfatoethyl.
Z1 and Z2 are preferably each independently of the other vinyl or xcex2-sulfatoethyl.
Z3 is preferably xcex2-chloroethyl or xcex2-sulfatoethyl, especially xcex2-chloroethyl.
Z4 is preferably xcex2-chloroethyl or xcex2-sulfatoethyl, especially xcex2-sulfatoethyl.
Preference is given to dyes of formula (1) wherein
D1 and D2 are each independently of the other a radical of formula (2a), (2b), (2c), (2d) or (2e), preferably of formula (2a) or (2e), and
R1 and R2 are hydrogen.
The radicals D1 and D2 in the dyes of formula (1) are identical or not identical.
The present invention relates also to a process for the preparation of dyes of formula (1), wherein
(i) approximately 1 molar equivalent of an amine of formula (5a)
D1xe2x80x94NH2xe2x80x83xe2x80x83(5a)
is diazotised in customary manner and reacted with approximately 1 molar equivalent of a compound of formula (6) 
xe2x80x83to form the compound of formula (7a) 
xe2x80x83and
(ii) approximately 1 molar equivalent of an amine of formula (5b)
xe2x80x83D2xe2x80x94NH2xe2x80x83xe2x80x83(5b)
is diazotised in customary manner and reacted with approximately 1 molar equivalent of the compound of formula (7a) obtained according to (i), to form the compound of formula (1) wherein the definitions and preferred meanings given above for each of D1, D2, R1 and R2 apply.
The diazotisation of the amines of formulae (5a) and (5b) is carried out in a manner known per se, for example with a nitrite, e.g. with an alkali metal nitrite, such as sodium nitrite, in a mineral acid medium, e.g. in a hydrochloric acid medium, at temperatures of, for example, from xe2x88x925 to 40xc2x0 C., preferably from 0 to 20xc2x0 C.
Coupling to the coupling components of formulae (6) and (7a) is carried out in a manner known per se, at acid, neutral or weakly alkaline pH values, for example at a pH value of from 0 to 8, and at temperatures of, for example, from xe2x88x925 to 40xc2x0 C., preferably from 0 to 30xc2x0 C.
The first coupling (i) is effected in an acid medium, for example at a pH value of from 0 to 4, and the second coupling (ii) is effected at a higher pH value, in a weakly acid, neutral or weakly alkaline medium, for example at a pH value of from 4 to 8.
If the same procedure as described above is used, except that, instead of using 1 molar equivalent of an amine of formula (5a) and 1 molar equivalent of an amine of formula (5b), there are used in each of the process steps (i) and (ii) approximately 1 molar equivalent of a mixture of at least two, but preferably two, non-identical amines, for example a 1:1 molar mixture of the compounds of formulae (5a) and (5b), there are then obtained first, according to (i), a mixture of the compounds of formulae (7a) and (7b) 
and, on further reaction of the mixture of the compounds of formulae (7a) and (7b), according to (ii), a mixture of dyes of formulae (1a), (1b), (1c) and (1d) 
The present invention accordingly relates also to dye mixtures comprising at least one dye of formulae (1a) and (1b) together with at least one dye of formulae (1c) and (1d), especially one dye of each of formulae (1a), (1b), (1c) and (1d), wherein the definitions and preferred meanings given above for each of D1, D2, R1 and R2 apply and D1 and D2 are not identical.
Preferably, in the dye mixtures according to the invention, D1 is a radical of formula (2a*) 
and D2 is a radical of formula (2a**) 
wherein
R3b and R3c are each independently of the other hydrogen, methyl or methoxy, especially hydrogen, and
Z1a and Z1b are each independently of the other vinyl or xcex2-sulfatoethyl, especially xcex2-sulfatoethyl, and
R1 and R2 are hydrogen.
The ratio of the dyes of formulae (1a), (1b), (1c) and (1d) in the mixture can vary within wide ranges and will depend upon the ratio of the amines D1xe2x80x94NH2 and D2xe2x80x94NH2 used according to each of (i) and (ii).
The dye mixtures mentioned above contain, for example, from 5 to 95% by weight, especially from 10 to 90% by weight, and more especially from 20 to 80% by weight, of a dye of formula (1a) and/or (1b), based on the total amount of the dyes of formulae (1a), (1b), (1c) and (1d) in the mixture.
The compounds of formulae (5a), (5b) and (6) are known or can be obtained in a manner known per se.
The present invention relates also to dye mixtures comprising at least one dye of formula (1) together with at least one dye of formula (8) 
wherein
r and s are each independently of the other the number 0 or 1 and
X2 and X3 are each independently of the other a radical of formula (3a), (3b), (3c) or (3d)
xe2x80x94SO2xe2x80x94Zxe2x80x83xe2x80x83(3a),
xe2x80x94CONHxe2x80x94(CH2)nxe2x80x94SO2xe2x80x94Zxe2x80x83xe2x80x83(3b),
xe2x80x94NHxe2x80x94COxe2x80x94CH(Hal)xe2x80x94CH2xe2x80x94Halxe2x80x83xe2x80x83(3c)
or
xe2x80x94NHxe2x80x94COxe2x80x94C(Hal)xe2x95x90CH2xe2x80x83xe2x80x83(3d),
xe2x80x83and
n is the number 2, 3 or 4,
Hal is halogen and
Z is vinyl or a radical xe2x80x94CH2xe2x80x94CH2xe2x80x94U and U is a group removable under alkaline conditions.
The definitions and preferred meanings given above for each of n, Hal and U apply.
The reactive dyes of formulae (1) and (8) contain sulfo groups, which may in each case be present either in the form of the free sulfo acid or, preferably, in the form of a salt thereof, for example in the form of a sodium, lithium, potassium or ammonium salt or in the form of a salt of an organic amine, e.g. in the form of a triethanolammonium salt.
The reactive dyes of formulae (1) and (8) and accordingly the dye mixtures may also comprise further additives, for example sodium chloride or dextrin.
Instead of the dye of formula (1), the dye mixtures according to the invention preferably comprise the above-mentioned mixtures of at least one dye of formulae (1a) and (1b) together with at least one dye of formulae (1c) and (1d), especially a compound of each of formulae (1a), (1b), (1c) and (1d), wherein the definitions and preferred meanings given above for the radicals D1, D2, R1 and R2 in the compounds of formulae (1a), (1b), (1c) and (1d) apply.
The dye of formula (8) in the dye mixture according to the invention is preferably a dye of formula (8a), (8b) or (8c) 
especially of formula (8a),
wherein
one of the substituents G1 and G2 is amino and the other is hydroxy,
X2a, X3a and X3b are each independently of the others xcex2-sulfatoethylsulfonyl or vinylsulfonyl and
X2b, X2c and X3c are each independently of the others xcex1,xcex2-dibromopropionylamino or xcex1-bromoacryloylamino.
Especially preferred dye mixtures according to the invention comprise a compound of each of formulae (1a), (1b), (1c) and (1d) together with a dye of formula (8a).
The dye of formula (1) or the dyes of formulae (1a), (lb), (1c) and (1d) are present in the dye mixture according to the invention in a weight ratio with respect to the dye of formula (8) of, for example, from 1:99 to 99:1, preferably from 5:95 to 95:5, and especially from 10:90 to 90:10.
The dye mixtures according to the invention may be prepared, for example, by mixing the individual dyes. The mixing process is carried out, for example, in a suitable mill, e.g. a ball or pin mill, and also in a kneader or mixer.
The dye mixtures according to the invention may comprise, in addition to the reactive dyes mentioned above, further dyes, especially further reactive dyes for shade adjustment.
The dyes and dye mixtures according to the invention are fibre-reactive, that is they are capable of reacting with the hydroxyl groups of cellulose or with the reactive centres of natural and synthetic polyamides, with the formation of covalent chemical bonds.
The reactive dyes according to the invention and the mixtures of reactive dyes according to the invention are suitable for dyeing and printing a wide variety of materials, especially hydroxyl-group-containing or nitrogen-containing fibre materials. Examples include silk, leather, wool, polyamide fibres and polyurethanes, and especially all types of cellulosic fibre materials. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, and cellulose and regenerated cellulose. The dyes and dye mixtures according to the invention are also suitable for dyeing or printing hydroxyl-group-containing fibres contained in blend fabrics, for example blends of cotton and polyester fibres or polyamide fibres.
The dyes and dye mixtures according to the invention can be applied to the fibre material and fixed to the fibre in a number of ways, especially in the form of aqueous dye solutions or dye print pastes. They are suitable for the exhaust process and also for dyeing using the pad-dyeing process, can be used at low dyeing temperatures and require only short steaming times in the pad-steam process. The degrees of fixing are high and unfixed dye can be washed off readily, the difference between the degree of exhaust and the degree of fixing being remarkably small, that is to say the soaping loss is very small. The dyes and dye mixtures according to the invention are also suitable for printing, especially on cotton, but also for printing nitrogen-containing fibres, for example wool or silk or blend fabrics containing wool.
The dyeings and prints produced on cellulose fibre materials using the dyes and dye mixtures according to the invention have a high tinctorial strength and a high fibre-dye binding stability in both acidic and alkaline ranges, and they also have good fastness to light and very good wet-fastness properties, such as fastness to washing, water, seawater, cross-dyeing and to perspiration, as well as good fastness to pleating, to pressing, to rubbing, and especially to chlorine.